JPH02132161A - Surface-treated monoazolake pigment, production thereof and printing ink composition - Google Patents

Abstract

PURPOSE:To obtain the title monoazolake pigment consisting of a monoazolake pigment and free resin acid for treating the surface of the pigment, enhanced in transparency, vivid properties and dispersibility as well as surface tension of ink and having excellent printability such as flowability of ink. CONSTITUTION:The aimed monoazolake pigment obtained by adding (B) 3-30wt.% (as solid content of resin acid based on dye pigment) resin acid alkali salt solution to a monoazolake pigment obtained by subjecting (i) a soluble group-containing aromatic amine (e.g., 1-amino-4-methyl-benzene-2-sulfonic acid) to coupling and laking with (ii) beta-naphthols or beta-oxynaphthoic acids, improved in lipophilic properties as well as flowability and enhanced in apparent surface tension of ink.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Field of Application) The present invention relates to a surface-treated monoadzurake face It useful for various uses, particularly as a pigment for printing inks, and more specifically, to a surface-treated monoadzurake face It useful as a pigment for printing inks. This invention relates to a monoazo lake pigment that improves ink fluidity, a method for producing the same, and a printing ink composition obtained using the same.

(Conventional technology) Conventional. Monoazo lake pigments, which are made by coupling an aromatic amine with a soluble group as a diazo component and betaoxynaph-1, engineered acid, betanaphthol, etc. as a casobar component, are widely used in various applications such as printing inks, paints, and coloring of plastics. ing. These monoazo lake pigments have a transparent color tone. To make it clearer. In addition, to improve dispersibility, treatment is performed. This rosin treatment. Il! A resin acid alkaline salt solution (rosin soap) is usually added to the coupler component or dye. Then, a lake metal salt such as calcium chloride is added to precipitate an insoluble resin acid lake metal salt on the surface of the pigment.

The rosin-treated pigment obtained by Kitaki's conventional method improves the clarity and dispersibility of the pigment. When used in Off Sesoto stamp face 1 ink, there were some aspects that deteriorated the printability, such as a decrease in fluidity and a decrease in the surface tension of the ink.

(Problems to be Solved by the Invention) Therefore, in the present invention, an aromatic amine having a soluble group is used as a diazine component, and hetaoxynaphthoic acid.
Transparency in monoazo lake pigments made by coupling betanaphthol etc. as a coupler component. The object of the present invention is to provide a rosin-treated pigment that does not adversely affect printability without impairing improvements in clarity, dispersibility, etc., and a method for producing the same.

[Structure of the invention]

(Means for Solving the Problems) That is, the present invention combines a diazo component obtained by diazating an aromatic amine having a fusible group and a coupler component selected from betanaphthols and betaoxynaphthoic acids. , a monoazo lake pigment made into a lake,
A surface-treated monoazo lake pigment consisting of a free resin acid surface-treated on the pigment, and a diazo component obtained by diazotizing an aromatic amine having a soluble group. A dye solution or the dye obtained by campling a coupler component selected from betaphthols and betaoxynaphthoic acids? 9? A resin acid alkali salt solution is added to the pigment slurry which has been made into a lake, and if it has not been made into a lake, it is made into a lake, and then an acid is added to the system containing the resulting pigment and a resin acid alkali salt or a resin acid lake metal salt. The present invention also includes a method for producing a monoazo lake pigment surface-treated with a free resin acid obtained by adding a free resin acid, and a printing ink composition containing the surface-treated monoazo lake pigment and a vehicle for printing ink.

As the aromatic amine having a soluble group used in the present invention, for example, ■-amino-4-methylbenzene-
2-Sulfonic acid (common name p-1-luidine m-sulfonic acid). 1-amino-4-methyl-5-chlorobenzene-2
-sulfonic acid, 1-amino-4-chloro-5-methylbenzene-2-sulfonic acid, l-amino-4-methylbenzene-3-sulfonic acid, 1-amino-3-methyl-4
-Sulfonic acids, etc.

Typical coupler components include hetaoxynaphthoic acid or hetanaphthoic acid, but other oxynaphthoic acids, such as lower alkyl groups, alkoxy groups, or... Hetaoxynaf substituted with a halogen atom], engineering acid, etc. may also be used. Note that a coupler component other than betaoxynaphthoic acid can also be used in part for the 7-petaoxynaphthoic acid.

The monoazole lake pigment of the present invention using the above-mentioned raw materials can be produced according to a conventionally known method for producing monoazole lake pigments. That is, an aromatic amine having 5 soluble groups is diazotized according to a conventional method, while a precipitate solution is prepared from the above-mentioned canoplar component according to a conventional method, and both are brought together according to a conventional method. The pH of the system at this time is 7.5~
12.5 alkaline. After casobling, a lake forming agent (metal salt) is added to the dye solution to form a lake. Another adjustment method (7) is to add a lake forming agent to the diazo component in advance and then couple the component. Calcium is a laked metal. Barium, strontium. There are manganese etc.

What is the resin acid in the present invention? natural rosin acid, tall oil rosin acid, gum rosin acid, Uso F rosin acid, etc.), modified rosin acid (hydrogenated rosin acid, disproportionated rosin acid, polymerized rosin acid, fumarized [1 Synthetic resin acids (styrene acrylic acid, styrene maleic acid, copolymers thereof, partially esterified products, etc.).

The resin acid alkali metal salt solution of the present invention is water containing resin acid sodium/lium salt, resin acid potassium salt, etc. B is liquid.

Resin acid alkali metal salt aqueous solution. Should I add it to the casoblar component in advance? It is preferable to add it to the dye solution. It may also be added to the pigment slurry after it has been formed into a lake. If a resin acid alkali metal salt solution is added before forming a lake, a lake forming agent is added after the addition to form a lake. In this case, it is thought that the water-soluble resin acid alkali metal salt replaces the laked metal salt, becomes insolubilized, and coats the pigment surface.

The amount of resin acid alkali metal salt solution added is: The resin acid solid content is preferably 3 to 30% by weight based on the dye pigment.

The surface-treated monoazo lake pigment of the present invention can be produced by adding an acid to a system containing the pigment obtained above and a pigment coated with an alkali metal salt of resin acid or a lake metal salt of resin acid to adjust the pH to 5 to 3. can get.

Examples of acids that can be used include mineral acids such as hydrochloric acid and organic acids such as acetic acid.

In the present invention. Pigment slurry obtained by conventional method: heating,
Similar results can be obtained by reslurrying the press cake obtained by filtration and purification to adjust the pH of the system to about 3. In this case, it is preferable to perform the treatment at 40° C. or lower in order to prevent pigment crystal growth.

Vehicles for the printing ink of the present invention include, for example, rosin-modified phenolic resins, petroleum resins, and alkyl resins for offset ink. Alternatively, 20 to 50 parts by weight of these dry oil-modified resins, alni oil, tung oil. 30 parts by weight of vegetable oil such as soybean oil, n-paraffin, isoparaffin, aromatic oil. It consists of 10 to 60 parts by weight of a solvent such as naphthene or α-olefin.

The monoazo lake pigment of the present invention is blended into this offset ink vehicle. Other ink solvents, dryers,
Known additives such as a leveling improver and a thickener are appropriately blended to prepare a printing ink composition. Also. As a gravure ink. Gum mouth gin, wood mouth gin, tall oil rosin,
Calcified gin, lime gin ester, maleic acid resin. Gilsonite, Dammar, Cerasoc, polyamide resin. Vinyl resin, nitrosellulose. Cyclized rubber.
10 to 50 parts by weight of a resin mixture such as chlorinated rubber, ethyl cellulose, cellulose acetate, ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin, alkysod resin, etc. n-hexane, toluene. Ethanol, methanol. 30 to 80 parts by weight of a solvent such as acetone, ethyl acetate, ethyl lactate, cellosolve, diacetone alcohol, chlorobenzole, ethyl ether, acetal ethyl ether, ethyl acetoacetate, butyl cellosolve acetate, 3 to 35 parts by weight of the monoazo lake pigment of the present invention ．． Barium sulfate.
Barium carbonate, calcium carbonate, sesoko. Alumina white. Clay, silica, silica white talc, calcium silicate. It consists of 0 to 20 parts by weight of an extender pigment such as precipitated magnesium carbonate, and other adjuvants. It contains a plasticizer, an ultraviolet inhibitor, an antioxidant, an antistatic agent, etc. as appropriate.

Examples will be described below. In the examples, parts are parts by weight,
% represents weight %.

(Example) Example 1 1867 parts of p-toluidine-m-sulfonic acid was added to 300 parts of water.
1 part and 4 parts of sodium hydroxide.

Add 25 parts of 35% hydrochloric acid. After acid precipitation, add 200 parts of ice,
Cool to Q'C. 7 parts of sodium sulfite dissolved in 25 parts of water
Add part. The mixture is stirred for 30 minutes at 5°C or lower and is used as the diazo component.

On the other hand, 18.7 parts of betaoxynaphthoic acid was dissolved in a solution consisting of 1500 parts of water and 11 parts of sodium hydroxide.
The mixture cooled to 5°C is used as the casoblar component. The diazo component is added dropwise to the coupler component over a period of 20 minutes to perform a coupling reaction. After stirring for 30 minutes, 10% mouth gin soap 64
(15% resin solid content based on pigment content).
Adjust the pH to 12.3 with 1% aqueous sodium hydroxide solution. Next, 58 parts of a 35% lucium chloride aqueous solution was added and stirred for 92 hours to complete the lake formation reaction. 70℃
After heating, pass through the mouth and wash with water.
Resurry in 00 parts of water. Add 5% hydrochloric acid dropwise to the slurry. Adjust psummer1 to 3.0. The mixture was stirred at room temperature for 1 hour, filtered through the mouth, washed with water, dried, and ground. 49 parts of monoazole 1 pigment were obtained. For comparison, a pigment without acid treatment (conventional pigment) was also synthesized.

The contact angles of the pigment obtained in this example and the pigment obtained by the conventional method described above were compared. For water, the pigment obtained by the conventional method is 41', and the pigment obtained in this example is 41'.
It was 49°. Also, for methylene iodide. The angle of the pigment obtained by the conventional method is 23°, and the angle of the pigment obtained in this example is 19°.
Compared to conventional pigments, it was more hydrophobic and lipophilic. Also, if you measure the wet heat of water using a calorimeter.
The conventional pigment is 5. 1 cal/g, the pigment of this example had 3. It became hydrophobic at 0 cal/g.

The pigment obtained above was made into ink and tested. The varnish used was 50 parts of 36 liters of 7-nor (Arakawa Chemical's dirosine modified phenolic resin), 20 parts of linseed oil,
No. 5 Solvent (Nippon Oil Co., Ltd.: Ink solvent) 3
0 part was added and melted by heating at 200°C. Next. A gel varnish was prepared by adding 2 parts of aluminum octylate to 98 parts of this face.

70 parts of the obtained gel varnish, 20 parts of the above RN material, and 10 parts of No. 1 Solgent (Nippon Oil Co., Ltd.: ink solvent) were mixed and kneaded using a Miki roll. Offset ink was obtained.

There was no difference in dispersibility, hue, transparency, sharpness, etc. between the face rice obtained in this example and the pigment obtained in the conventional example, but the pigment in this example was different from the conventional Gn pigment. It has good fluidity compared to . No thickening over time was observed.

The pigments of this example and the conventional method were extracted with methanol, and the infrared absorption spectra of the extracts were measured. Pigments made using conventional methods. Absorption due to the carboxylic acid metal salt was observed at around 1540 cm-', whereas the pigment according to this example had absorption at around 1540 cm-'. The above absorption disappears. New 1700c
Absorption due to free carboxylic acid appeared near m-'.

Example 2 18.5 parts of p-}luidine-m-sulfonic acid and 4-
Methyl-aniline-3-sulfo/acid 0. 2 A portion was diazotized according to a conventional method, and a 35% calcium chloride aqueous solution 5
Add 8 parts to obtain a diazo solution. On the other hand, betaoxynaphthoic acid 1B. 7 parts were melted according to the usual method, and 106 parts of 10% mouth gin soap was obtained (25% resin solid content based on the pigment content).
Add to obtain the coupler liquid.

The diazo liquid was added dropwise to the casoblar liquid over a period of 20 minutes, and a coupling reaction and a lake formation reaction were carried out in the same manner as in Example 1.

Note that I) H at the end of rake formation was 12.0.

After stirring for 1 hour, 5% hydrochloric acid was added dropwise to adjust the pH to 3.0. Stir for 1 hour, filter through the mouth, wash with water, dry, and then crush. 5
Three parts of azo lake pigment were obtained. For comparison, a pigment without acid treatment (conventional pigment) was also synthesized. The offset ink prepared from the pigment of this example is. Compared to pigments obtained by conventional methods, the emulsification fluctuation of the ink (fluidity fluctuation when water is forcibly emulsified in the ink) is small, and the surface tension of the ink alone or LJ is increased. An increase in the surface tension of the emulsion was observed.

〔Effect of the invention〕

The surface-treated monoazo lake pigment obtained by the present invention has increased lipophilicity compared to the pigment obtained by the conventional method ζ.Therefore, the printing ink using the surface-treated monoazo lake pigment of the present invention has high fluidity. Also. - Fluidity fluctuations when water is forcibly emulsified in ink are also small, increasing the apparent surface tension of the ink. Moreover. The surface-treated monoazo lake pigment of the present invention has excellent pigment dispersibility. There is no discernible difference in transparency, sharpness, and hue from those obtained using conventional methods.

Thus, the surface-treated pigment according to the present invention... Traditional! 7
It has surface properties different from those of pigments treated with pigments. Excellent as a pigment for printing inks such as offset printing ink and gravure printing ink, as well as a coloring agent for paints, plastics, etc.

Claims (1)

[Claims] 1. Coupling a diazo component obtained by diazotizing an aromatic amine having a soluble group with a coupler component selected from betaphthols and betaoxynaphthoic acids,
A surface-treated monoazo lake pigment comprising a laked monoazo lake pigment and a free resin acid surface-treated on the pigment. 2. A dye solution obtained by coupling a diazo component obtained by diazotizing an aromatic amine having a soluble group with a coupler component selected from betaphthols and betaoxynaphthoic acids, or a pigment obtained by turning the dye solution into a lake. A resin acid alkali salt solution is added to the slurry, and if the slurry is not made into a lake, it is made into a lake, and then an acid is added to the system containing the resulting pigment and a resin acid alkali salt or a resin acid lake metal salt. A method for producing a monoazo lake pigment surface-treated with a free resin acid. 3. A printing ink composition comprising the surface-treated monoazo lake pigment according to claim 1 and a vehicle for printing ink.